Propellant for gas generators

ABSTRACT

A propellant for gas generators, especially for lifesaving systems, contains one or several tetrazole derivative(s) or respectively one or several compounds from the groups of (A) cyanic acid derivatives and their salts, (B) triazine and triazine derivatives, (C) urea, its salts, derivatives, and compounds evolved therefrom and their salts, wherein the aforementioned compounds can also be present as mixtures; and an oxidizing agent from the group of peroxides of zinc, calcium, strontium or magnesium or such peroxides with nitrates of ammonium, sodium, potassium, magnesium, calcium and iron, wherein it is possible to add further gas generating components, coolants, reducing agents, catalysts and/or porosity-producing media.

BACKGROUND OF THE INVENTION

[0001] Gas generators have become of increasing interest for lifesavingpurposes, for example in vehicles. Worldwide, the most popular mixturefor gas generation contains sodium azide. However, sodium azide istoxic, requiring special measures during the manufacture of the rawmaterial, during the preparation of the gas charge composition, andduring its processing, quality control, and waste removal. This holdstrue, in particular, in connection with the scrapping of vehicles.

[0002] There has been a large number of attempts to utilize substancesother than sodium azide. Thus, DE-A-2,142,578 describes a press-moldedpropellant charge for the rapid inflation of a hollow body by thereaction of tetrazylazene with oxygen carriers. DE-A-1,806,550 proposesa propellant charge which generates pressure gas, yielding cool gases,based on ammonium nitrate, activated carbon, and a compound that issubject to endothermal decomposition or sublimation. However, thissystem produces a large proportion of steam, representing a drawbacksince water leads to a strong increase in temperature due to its highheat of condensation.

[0003] DE-A-1,222,418 discloses mixtures generating pressurized gas,based on inorganic perchlorate oxidizers, polymeric fuel binders, and acoolant. Preparations having high proportions of chlorate orperchlorate, however, lead to chlorine components in the reaction gases.Thus, EP-A-372,733 likewise yields an unsatisfactory mixture inasmuch asthe propellant charge for the proposed airbag contains about 40%ammonium perchlorate. Even nitrocellulose and nitroglycerin compositionscan be found in the literature. Such suggestions cannot be consideredfor use in lifesaving systems. Nitrocellulose and nitroglycerinmixtures, or also other energetic compounds rich in carbon must beeliminated on account of carbon monoxide formation.

[0004] The propellant charges in DE-A-1,250,318, containingaminotetrazole, potassium dichromate, calcium resinate, and metallicsilicon, do not meet up-to-date safety requirements, either. The sameholds true for DE-C-2,004,620 wherein the compressed gas-producingcharges contain azotetrazole and/or ditetrazole and chlorates orperchlorates. The propellant charges of U.S. Pat. No. 3,734,789 whichcontain 5-aminotetrazole nitrate and polyisoprene birders, althoughburning up rapidly, also generate carbon monoxide owing to thecarbon-rich binder proportion, in health-endangering concentrations.

SUMMARY OF THE INVENTION

[0005] Accordingly, the invention is based on the object of makingavailable gas compositions, the manufacture and processing and/orhandling of which are harmless and the reaction products of which arenontoxic.

[0006] This object has been attained by a propellant or gas generatingcomposition for gas generators containing, as the nitrogenous compound,(a) tetrazole or one or more tetrazble derivative(s) of the followingformula I

[0007] wherein R₂ and R₂ or R₃ can be identical or different (but eitherR₂ or R₃ is present) and can be: hydrogen, hydroxy, amino, carboxy, analkyl residue of 1-7 carbon atoms, an alkenyl residue of 2-7 carbonatoms, an alkylamino residue of 1-10 carbon atoms, an aryl residueoptionally substituted by one or several substituents which can beidentical or different, selected from the amino group, the nitro group,the alkyl residues of 1-4 carbon atoms, or an arylamino residue whereinthe aryl residue can be optionally substituted, or their sodium,potassium, and guanidinium salts, or containing, as the nitrogenouscompounds,

[0008] (b) respectively one or several compounds from the groups of

[0009] (A) cyanic acid derivatives and their salts,

[0010] (B) triazine and triazine derivatives,

[0011] (C) urea, its salts, derivatives, and compounds evolved therefromand their salts,

[0012] wherein the compounds recited under (a) and (b) can also bepresent as mixtures,

[0013] and containing an oxidizing agent from the group of theperoxides, or from the group of the peroxides together with oxidizingagents from the group of the nitrates.

DETAILED DESCRIPTION OF THE INVENTION

[0014] By the formula I, applicants are referring to tetrazole orderivatives of tetrazole of either the 1-H or 2-H tautomeric forms asshown in the following formulae IA and IB, respectively:

[0015] The nitrogen-containing compounds to be used according to thisinvention are those forming, in a mixture with oxidizing agents, duringtheir thermal-chemical reaction, primarily CO₂, N₂ and H₂O, but notreleasing any gases, such as CO or NO_(X) in health-endangeringconcentrations. An especially significant feature resides in that theaddition of binders is not absolutely necessary.

[0016] R₁ preferably is hydrogen, amino, hydroxy, carboxy, a methyl,ethyl, propyl or isopropyl, butyl, isobutyl or tert-butyl, n-pentyl,n-hexyl or n-heptyl residue, a methylamino, ethylamino, dimethylamino,n-heptylamino, n-octylamino or n-decylamino residue, a phenylaminoresidue, or a phenyl or aminophenyl residue.

[0017] R₂ or R₃ is preferably hydrogen, a methyl or ethyl residue, or aphenyl or aminophenyl residue.

[0018] The following tetrazole derivatives are especially preferred:

[0019] 5-Aminotetrazole, sodium, potassium or calcium5-aminotetrazolate, 1-(4-aminophenyl)tetrazole,1-methyl-5-dimethylaminotetrazole, 1-methyl-5-methyl-aminotetrazole,1-methyltetrazole, 1-phenyl-5-aminotetrazole,1-phenyl-5-hydroxytetrazole, 1-phenyltetrazole,2-ethyl-5-aminotetrazole, 2-methyl-5-aminotetrazole,2-methyl-5-carboxytetrazole, 2-methyl-5-methylaminotetrazole,2-methyltetrazole, 2-phenyltetrazole, 5-(p-tolyl)tetrazole,5-diallylaminotetrazole, 5-dimethylaminotetrazole,5-ethylaminotetrazole, 5-hydroxytetrazole, 5-methyltetrazole,5-methylaminotetrazole, 5-n-decylaminotetrazole,5-n-heptylaminotetrazole, 5-n-octylaminotetrazole, 5-phenyltetrazole,5-phenylaminotetrazole, or bis(aminoguanidine)azotetrazole.

[0020] Cyanic acid derivatives used with preference are sodium cyanate,cyanuric acid, 1-cyanoguanidine and/or disodium cyanamide; triazinederivatives used with preference are 1,3,5-triazine, cyanuric acidesters and/or cyanuric acid amide (melamine); and urea derivatives usedwith preference are biuret, guanidine, nitroguanidine, guanidinenitrate, aminoguanidine, aminoguanidine nitrate, triaminoguanidinenitrate, aminoguanidine hydrogen carbonate, azodicarboxylic aciddiamide, dicyandiamidine nitrate, dicyandiamidine sulfate, tetrazeneand/or semicarbazide nitrate.

[0021] Besides being acceptable from health viewpoints, the mixturesaccording to this invention exhibit a high thermal and weatherstability, which is a prerequisite for perfect action even afterlong-term storage.

[0022] Suitable oxidizing agents are nitrates of ammonium, sodium,potassium, magnesium, calcium or iron, preferably sodium nitrate, orperoxides of zinc, calcium, strontium or magnesium.

[0023] The peroxides are used with an oxygen value as obtainable fromstable compounds. For zinc peroxide, this value is about 11 to 14% byweight. The corresponding molar ratio of nitrogen-containing compound toperoxide is in a range from 1:2 to 5.5. Calcium peroxide can exhibit anactive oxygen value of, for example, 18.26% by weight, and grain sizesof 15.5 μm and is advantageously utilized in a molar ratio ofnitrogen-containing compound/peroxide of 1:3. In general, theaforementioned peroxides can be used in a molar ratio ofnitrogen-containing compound to peroxide in a range of 1:1 to 20.

[0024] Calcium peroxide and/or zinc peroxide is used with preference. Itis also possible to employ mixtures of the peroxides with one another ormixtures with other oxidizing agents. Other oxidizing agents are, forexample, the above-mentioned nitrates of ammonium, sodium, potassium,magnesium, calcium or iron, preferably sodium nitrate.

[0025] When using magnesium peroxide and, in particular, calcium orstrontium peroxide, the alkaline-acting hydrolysis products may evokereactions with the other components of the mixture. In this case,coating of the peroxides with inorganic or organic materials inaccordance with conventional methods is suitable. Such a coating offers,moreover, the advantage of improved handling ability since thethus-treated propellant will no longer be dusty.

[0026] The mixtures to be utilized according to this invention of thetetrazole and/or its derivatives with the compounds from groups (A), (B)and/or (C) permit a finely graded staggering of the propellants withregard to their reaction rate and the thus-formed vapors and gases. Thisis a staggering needed for providing a maximum variety of uses for thepropellant charges of this invention. Depending on the given structureof the generator housing of an airbag, for example, or of a belttightening device, the propellant charges of this invention must beblended in a controlled fashion. Only in this way is it possible toattain an effect that is at an optimum in each case. The degree ofefficiency of the propellant charges according to this invention is,after all, affected not only by the composition, but furthermore by theignition, and also by the tamping resulting from the construction, andby the flow-off behavior of the thus-evolving vapors and gases.Evaluation of the degree of efficiency can be accomplished, for example,by determination of the gas pressure rise gradient of the respectivemixture in the given external environment in each case dependent on thestructure, and the type of ignition selected. The thus-formed gasconcentrations, especially those of the toxic gases, must not exceedspecific maximum values. These values result from the MAK (maximaleArbeitsplatzkonzentration=maximum working site concentration) values (orTLV (threshold-limit value) values in the United States). Technicalrequirements are derived from these values in conjunction with theexposure times permitted and must be met by the respective propellantcharges. When determining these requirements, the differing passengercells, for example, also enter into the consideration. In order tofulfill these demands, the respective propellant charge must be mixed incontrolled fashion.

[0027] The values indicated in the tables were determined by igniting,in a cup in a loose bulk, 4 g of the respective propellant charge bymeans of a hot wire in a pressurized bomb tube having a volume of 25 ml.After ignition, a pressure-time curve was recorded. The thus-obtainedvalues were evaluated as follows:

[0028] (1) Maximum pressure (bar): with the weighed-in amounts being thesame, differences can be ascribed directly to the thus-produced gasvolumes. These are determined by gas yield and thermal content of thereaction.

[0029] (2) Rise in gas pressure for the range of 40-60% of maximumpressure: In this region, the curve is no longer falsified by theignition and/or the cooling-off characteristic of the vapors by theinner surface of the bomb tube. The indicated times in milliseconds (ms)represent the pressure rise and signify differing reaction rates. Suchvalues are also obtained in the respective cases of application, forexample in the diverse, structurally modified, gas generator housings.They permit a precise tuning of the propellant charges of this inventionwith a view toward the efficiency requirements. By the indication of thepressure rise times in a range of 40-60% of the maximum pressure, thereaction rate of the propellant charges of the invention is adequatelycharacterized. The time periods for the reaction until the occurrence ofmaximum pressure serve as additional information.

[0030] The gas temperature can be kept low in a controlled fashion byaddition of diammonium oxalate, oxalic acid diamide, dicyandiamide, orcarbonates and, respectively, bicarbonates. If thermal stability is nota factor, and smoke formation upon addition of inorganic carbonates orbicarbonates is to be avoided, it is possible to use aminoguanidinebicarbonate as the organic bicarbonate. Other additives can beconstituted by oxalic acid or urea, generally added in an amount of upto 5% by weight, based on the mixture.

[0031] Suitable reducing agents are metal powders of iron, magnesium,zirconium or titanium which, in contrast to the nonmetallic compoundboron, have no strong effect on the deflagration velocity, but in caseof the latter do have an influence on the heat production of thereaction and on the reaction products. The proportion of the reducingagents can amount to up to 5% by weight.

[0032] Suitable catalysts for a mixture of such heterogeneouscomposition are compounds having an effect on the decomposition ofperoxides, such as, for example, metals or their oxides, e.g. manganesedioxide. Additions of vanadium pentoxide or cerium dioxide lead to anincrease in the reaction velocity. When adding up to 5% by weight ofmolybdenum(VI) oxide, the velocity is only slightly changed, and thisalso applies in the presence of cerium(III) nitrate hexahydrate. Theseadditives are effective in amounts of up to a few percent by weight.Further catalysts are metal complexes, of which ferrocene can here becited as an example; the addition of this compound with up to about 3%by weight markedly raises the reaction velocity.

[0033] The gas compositions described in accordance with this inventionare manufactured by mixing the components according to conventionalmethods, optionally with the preparation of a harmless premix to whichadditional components are added. This mixture can already be utilized inpowdered form. Unmixing on account of varying densities of thecomponents can be counteracted by granulation of the mixture.

[0034] In the majority of applications by far, the mixture will beformed by press-molding or similar measures. To simplify this procedure,press-molding aids can be added to the mixture. Suitable as such aregraphite, molybdenum disulfide, “Teflon”, talc, zinc stearate or boronnitride. These agents have an effect even in minimum quantities andaffect the properties and deflagration behavior either not at all oronly to a minor extent.

[0035] It may be advantageous in some cases to influence thedeflagration characteristic of the press-molded item by producingporosity. Such a method resides in admixing additives, such as salts, tothe mixture prior to the actual shaping step; these additives can beremoved again after molding by extraction with water or solvents.Another method resides in adding materials of low thermal resistancewhich decompose when the molded item is heated. The surface of themixture can also be enlarged by adding to the mixture, prior topress-molding, hollow microspheres of glass or synthetic resins. Thedensity of the press-molded article that can be attained thereby candeviate by approximately up to 20% from that of the untreatedpress-molded article; in this connection, this value is to be merely aroughly governing value and does not represent a limitation. Thistreatment leads to an extreme acceleration of the deflagration process.

[0036] A further treatment of the molded articles can consist in surfacecoating. In this case, besides achieving an effect on the deflagrationcharacteristic, protection against environmental influences is obtained,in particular. Such a measure can also be suitable for increasing thestrength of the molded item. In extreme cases, the use of suitablefibers for stabilization purposes would have to be additionally providedfor. A side effect of the coating procedure is a decreased abrasion ofthe items during transport stresses.

[0037] The thus-treated molded articles can be introduced in loose bulkor in oriented fashion into appropriate pressure-proof containers. Theyare ignited according to conventional methods with the aid of initiatorcharges or thermal charges wherein the thus-formed gases, optionallyafter flowing through a suitable filter, lead to inflation of thelifesaving system within fractions of a second.

[0038] The propellants of this invention are especially suited forso-called airbags, impact bags which are utilized in automotive vehiclesor airplanes for occupants' protection. In case of vehicle impact, theairbag must fill up within a minimum time period with gas quantities ofabout 50 to 300 liters, depending on system and automobile size. Thepropellants of this invention are likewise suitable for use inbelt-tightening devices.

[0039] Lifesaving systems containing the propellants of this inventionlikewise form the subject matter of the present invention.

EXAMPLE 1

[0040] 167 g of 5-aminotetrazole (5-ATZ) (produced from aminoguanidinesulfate, sodium nitrite and nitric acid) is recrystallized from about600 ml of water under continuous agitation, dried at 110° C. afterfiltration, ground up, and separated from coarse proportions with a 250gm screen (5-ATZ specification: mp/decomp.: >203° C., average grain size80 μm and H₂O proportion <0.05%). From ZnSO₄×7H₂O and hydrogen peroxidein aqueous ammonia, ZnO₂ is produced, washed with dilute acetic acid aswell as water, and dried at 60° C. (specification of ZnO₂: 13.47% byweight of active oxygen, average grain size 20.3 μm).

[0041] 5-ATZ and ZnO₂, as the components for nontoxic gas charges, arehomogenized together in a weight ratio of 1 to 7 (corresponding to amolar ratio of about 1:5) in plastic containers in a tumbler mixer for1-2 hours. Of this sample, 3.0 g is made to react in bulk in a 25 mlsize stainless steel bomb tube by means of an electrically heatable Fewire, and the pressure-time curve is recorded by means of apiezoelectric measuring device. After about 30 ms, a maximum gaspressure of about 200 bar is produced, due primarily to the formation ofCO₂, N₂, O₂ and H₂O. The reaction has a strongly exothermal character ofabout 471 cal/g (about 1970 J/g). ZnO remains as the reaction residue.The CO proportion corresponds to requirements. The deflagration point isat 219° C., the friction sensitivity is at 240 N, the impact sensitivityis at 20 J.

EXAMPLES 2-24

[0042] The use of 5-ATZ and ZnO₂ as components in nontoxic gas chargescorresponds to Example 1 with the use of further additives. Examples2-24 below describe the reaction of other mixtures produced byconventional procedures. The results are compiled in Tables 1-4.

[0043] In the Tables, the first comment in the column labeled “ReactionVelocity” refers to Example No. 2, the second to Example No. 3 and soon. TABLE 1 Reaction Velocity Organic Additives (Noles) (as Measured inExample No. 2 3 4 5 6 7 8 9 10 Example 1) 5-Aminotetrazole 1 1 1 1 1 1 11 1 Zinc peroxide 3 3 3 3 3 3 3 3 3 Ammonium nitrate 2.5 2.5 2.5 2.5 2.52.5 2.5 2.5 2.5 Rose as compared with 1 Aminoguanidine nitrate 1 Rose ascompared with 2 Urea 1 Dropped as compared with 2 Oxalic acid dihydrate1 Dropped as compared with 2 Oxalic acid diamide 1 Dropped as comparedwith 2 Diammonium oxalate 1 Dropped as compared monohydrate with 2Semicarbazide nitrate 1 Rose as compared with 2 Aminoguanidinebicarbonate 1 Dropped as compared with 2 Ferrocene 1 × 10⁻³ Rose ascompared with 2

[0044] TABLE 2 Reaction Velocity Inorganic Additives (Moles) (asMeasured in Example No. 11 12 13 14 15 16 Example 1) 5-Aminotetrazole 11 1 1 1 1 Zinc peroxide 3 3 3 3 3 1.5 Ammonium nitrate 1.5 2.5 2.5 2.5Iron nitrate nonahydrate 1.6 · 10⁻² Dropped as compared with 2 Zinccarbonate 2 · 10⁻³ Dropped as compared with 2 Molybdenum(VI) oxide3 · 10⁻³ Comparable to 2 Sodium nitrate 1 Dropped as compared with 2Strontium nitrate 1 Dropped as compared with 2 Calcium peroxide 1.5Comparable to 2

EXAMPLE 25

[0045] The gas charge mixtures described in Examples 1-24 can also beutilized in press-molded form. A mixture of 10 g of 5-ATZ (H₂Oproportion <0.1%, mp [decomposition]>203° C., grain size 200-250 gm),43.9 g of ZnO₂ (12.85% by weight of active oxygen, grain size about 14μm) and 23.5 g of NH₄NO₃ (mp 167-169° C., grain size 250-315 μm), molarratio 1:3:2.5, is blended in accordance with Example 1 and pressed intotablets (diameter=6 mm, height=2.77 mm, density=2.18 g/CM³, radialpressure force=155.5±28.4 N) with a pressure of 4 tons. The deflagrationbehavior of the press-molded items, as tested in correspondence withExample 1, is slower than that of the bulk material and requires 0.1 gof B/KNO₃ or Ti/ZnO₂ as initiating mixture. The reaction velocity riseswith a drop in the pressing force and drops with the size of the pressedmaterial. The residue from the reactions remains extensively preservedin the form of the pressed items.

EXAMPLES 26-32

[0046] As described in Example 1, further mixtures were prepared fromgas-generating components and oxygen-yielding compounds, such as zincperoxide, with an active oxygen proportion of 13.07% by weight and anaverage grain size of 11.8 μm or, in case of sodium nitrate, with anaverage grain size of <45 μm.

[0047] Table 4 below contains additional data on the mixtures. TABLE 4Melting Point Molar Ratios or Mixture Component (° C.) 26 27 28 29 30 3132 5-Aminotetrazole 206-208 1 Potassium 5-aminotetrazolate 269 1 Bis(aminoguanidine)- 224-226 1 azotetrazole Nitroguanidine 252 1 Guanidinenitrate 210-214 1 Semicarbazide nitrate 115-119 1 1-Cyanoguanidine208-210 1 Zinc peroxide 200 (decomp.) 2.48 2.48 10.64 1.42 1.42 0.714.25 Sodium nitrate — 0.83 0.83 3.55 0.47 0.47 0.24 1.42

[0048] The components were homogenized in containers of plastic for a ½hour with a tumbler-mixer, a ½ hour with a vibrator, and again for a ½hour with a tumbler-mixer.

[0049] Of the thus-homogenized mixture, 4 g was introduced as describedin Example 1 into a stainless steel pressure bomb tube and, under seal,made to react upon ignition with an incandescent wire. The followingitems were measured:

[0050] the arising pressure (bar) up to the maximum value,

[0051] the time (milliseconds, ms) up to maximum pressure value,

[0052] the pressure increase gradient (dp/dt) between a pressurereaching 40-60% of the maximum pressure value. The rise time served asthe yardstick.

[0053] Table 5 below shows the values for the maximum pressure (bar) andthe time in ms up to maximum pressure, ranging within regions asdescribed in Example 1 for a gas charge of 5-aminotetrazole and zincperoxide. In addition, the time between 40 and 60% of maximum pressurewas determined. TABLE 5 Max. Time (ms) Example Pressure to Max. to40-60% of No. (bar) Pressure Max. Pressure 26 359 30 1.2 27 217 123 13.128 352 29 1.5 29 473 39 1.3 30 549 14 0.5 31 917 7 0.2 32 148 220 20.1

[0054] By adaption of the parameters and admixture of furthercomponents, it is possible to set the specifications required for therespective gas charge.

[0055] Another sample of the previously recited mixtures was studiedwith regard to physical and safety properties. The results are set forthin Table 6. TABLE 6 Deflagration Friction Impact Heat of Ex PointSensitivities Explosion No. (° C.)* (N) (J) (J/g) 26 180 >360 7.5 245127 207 >360 10 2293 28 197 >360 4 2411 29 215 >360 20 2964 30 364 >36015 2777 31 210 >360 2 3128 32 194 >360 30 2101

[0056] The components are suitable for the production of gas charges onaccount of their miscibility, processability, press-molding ability forshaping, as well as compatibility with one another and with otheradditives, as well as due to their characteristic safety data.

EXAMPLES 33-44

[0057] As described in Examples 26-32, the mixtures of Examples 33-44were produced from zinc peroxide (active oxygen proportion 12.0% byweight, average grain size 4.8 μm), aminotetrazole (average grainsize≦125 μm), sodium nitrate (grain size≦45 μm), and the listedcomponents with a grain size of <125 μm.

[0058] The friction sensitivity, measured according to the method ofBAM, was in all cases >360 N. The additionally listed components aredisclosed in the literature.

[0059] Tables 7 and 8 below contain additional data on the mixtures.TABLE 7 % by Molar Formulations Wt. Proportions Ex.No. 33 5-ATZ 29.8 1.4Zinc peroxide 23.4 0.75 Sodium nitrate 46.8 2.2 Ex.No. 34 5-ATZ 19.5 1.0Dicyandiamidine nitrate 15.2 0.4 Zinc peroxide 21.5 0.75 Sodium nitrate43.8 2.24 Ex.No. 35 5-ATZ 18.1 1.0 Dicyandiamidine sulfate 12.8 0.2 zincperoxide 19.8 0.75 Sodium nitrate 49.3 2.73 Ex.No. 36 5-ATZ 19.5 1.01-Cyanoguanidine 7.7 0.4 Zinc peroxide 21.4 0.75 Sodium nitrate 51.42.64 Ex.No. 37 5-ATZ 16.9 1.0 Melamine 10.0 0.4 Zinc peroxide 18.6 0.75Sodium nitrate 54.5 3.22 Ex.No. 38 5-ATZ 20.2 1.0 Azodicarboxylic acid11.0 0.4 diamide Zinc peroxide 22.2 0.75 Sodium nitrate 46.6 2.31 Ex.No.39 5-ATZ 19.6 1.0 Cyanuric acid 11.9 0.4 Zinc peroxide 21.4 0.75 Sodiumnitrate 47.1 2.41 Ex.No. 40 5-ATZ 22.5 1.0 Urea 6.4 0.4 Zinc peroxide24.7 0.75 Sodium nitrate 46.4 2.06 Ex.No. 41 5-ATZ 20.2 1.0 Biuret 9.80.4 Zinc peroxide 22.2 0.75 Sodium nitrate 47.8 2.37 Ex.No. 42 5-ATZ21.0 1.0 Aminoguanidine nitrate 13.5 0.4 Zinc peroxide 23.0 0.75 Sodiumnitrate 42.5 2.03 Ex.No. 43 5-ATZ 20.5 1.0 Sodium dicyanamide 8.6 0.4Zinc peroxide 22.5 0.75 Sodium nitrate 48.4 2.37 Ex.No. 44 5-ATZ 23.91.0 Sodium cyanate 7.3 0.4 Zinc peroxide 26.2 0.75 Sodium nitrate 42.61.79

[0060] TABLE 8 Gas Pressure Rise for Range of Heat of Impact MixtureComponents Zinc 5-Amino- Sodium 40-60% P_(max) Maximum ExplosionSensitivity Deflagration Example in Molar Proportions Peroxide tetrazoleNitrate (ms) Pressure (bar) (J/g) (J) point (° C.) No. 0.75 1.4 2.2 0.38683 3528 5 >400 33 Dicyandiamidine nitrate 0.4 0.75 1.0 2.24 0.40 7613142 6 >400 34 Dicyandiamidine sulfate 0.2 0.75 1.0 2.73 1.04 656 28837.5 395 35 1-Cyanoguanidine 0.4 0.75 1.0 2.64 0.36 661 3038 10 367 36Melamine 0.4 0.75 1.0 3.22 1.16 652 3187 10 >400 37 Azodicarboxylic acid0.4 0.75 1.0 2.31 0.36 706 3191 6 >400 38 diamide Cyanuric acid 0.4 0.751.0 2.41 0.80 582 2732 7.5 >400 39 Urea 0.4 0.75 1.0 2.06 0.40 654 305310 >400 40 Biuret 0.4 0.75 1.0 2.37 0.56 663 2982 7.5 363 41Aminoguanidine nitrate 0.4 0.75 1.0 2.03 0.30 693 3190 7.5 256 42 Sodiumdicyanamide 0.4 0.75 1.0 2.37 0.36 486 3226 7.5 356 43 Sodium cyanate0.4 0.75 1.0 1.79 0.34 458 3005 10 349 44

1. A propellant composition for producing reaction products not havingtoxic gases in health-endangering concentrations in gas generators, thecomponents of the composition consisting essentially of: at least onenitrogen-containing compound selected from the group consisting of (A) acyanic acid derivative selected from the group consisting of sodiumcyanate, cyanuric acid, 1-cyanoguanidine, disodium cyanamide and a saltof disodium cyanamide, (B) triazine or triazine derivative selected fromthe group consisting of cyanuric acid ester, cyanuric acid amide, and asalt of disodium cyanamide, and (C) urea, its salts and a ureaderivative selected from the group consisting of biuret, guanidine,nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidinenitrate, aminoguanidine hydrogen carbonate, azodicarboxylic aciddiamide, dicyandiamidine nitrate, dicyandiamidine sulfate, tetrazene,and semicarbizide nitrate; and an oxidizing agent comprising aninorganic peroxide or comprising a mixture of an inorganic peroxide anda nitrate; wherein the reaction products of the propellant compositiondo not contain toxic gases in health-endangering concentrations.
 2. Apropellant composition according to claim 1, wherein the reactionproducts of the propellant composition do not contain toxic gases inexcess of at least one of MAK and TLV values.
 3. A propellantcomposition for producing reaction products not having the toxic gasesin health-endangering concentrations in gas generators, the componentsof the composition consisting essentially of: (1) at least onenitrogen-containing compound selected from the group consisting of (a)tetrazole or a tetrazole derivative of the formulae IA or IB:

 wherein R₁ and R₂ or R₃ are identical or different and are hydrogen,hydroxy, amino, carboxy, an alkyl residue of 1-7 carbon atoms, analkenyl residue of 2-7 carbon atoms, an alkylamino residue of 1-10carbon atoms, an aryl residue, an arylamino residue, a substituted arylresidue or a substituted arylamino residue, the substituted aryl residueor substituted arylamino residue being substituted by one or severalsubstituents which are identical or different, and which are selectedfrom the group consisting of an amino group, a nitro group and an alkylgroup of 1-4 carbon atoms or a sodium, a potassium or a guanidinium saltof said tetrazole or tetrazole derivative, and (b) at least one compoundselected from the group consisting of (A) a cyanic acid derivativeselected from the group consisting of sodium cyanate, cyanuric acid,1-cyanoguanidine, disodium cyanamide and a salt of disodium cyananide,(B) triazine or triazine derivative selected from the group consistingof cyanuric acid ester, cyanuric acid amide, and their salts, and (C)urea, its salts and a urea derivative selected from the group consistingof biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine,aminoguanidine nitrate, aminoguanidine hydrogen carbonate,azodicarboxylic acid diamide, dicyandiamidine nitrate, dicyandiamidinesulfate, tetrazene, and semicarbizide nitrate; and (2) an oxidizingagent comprising a peroxide or comprising a mixture of a peroxide and anitrate; wherein the reaction products of the propellant composition donot contain toxic gases in health-endangering concentrations.
 4. Apropellant composition according to claim 3, wherein the reactionproducts of the propellant composition do not contain toxic gases inexcess of at least one of MAK and TLV values.
 5. A propellantcomposition for producing reaction products not having toxic gases inhealth-endangering concentrations in gas generators, the components ofthe composition consisting essentially of: (1) at least onenitrogen-containing compound selected from the group consisting of (a)tetrazole or a tetrazole derivative of the formulae

 wherein R₁ and R₂ or R₃ are identical or different and are hydrogen,hydroxy, amino, carboxy, an alkyl residue of 1-7 carbon atoms, analkenyl residue of 2-7 carbon atoms, an alkylamino residue of 1-10carbon atoms, an aryl residue, an arylamino residue, a substituted arylresidue or a substituted arylamino residue, the substituted aryl residueor substituted arylamino residue being substituted by one or severalsubstituents which are identical or different, and which are selectedfrom the group consisting of an amino group, a nitro group and an alkylgroup of 1-4 carbon atoms or a sodium, a potassium or a guanidinium saltof said tetrazole or tetrazole derivative, and (b) at least one compoundselected from the group consisting of (A) a cyanic acid derivativeselected from the group consisting of sodium cyanate, cyanuric acid,1-cyanoguanidine, disodium cyanamide and a salt of disodium cyanamide,(B) triazine or triazine derivative selected from the group consistingof cyanuric acid ester, cyanuric acid amide and their salts, and (C)urea, its salts and a urea derivative selected from the group consistingof biuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine,aminoguanidine nitrate, aminoguanidine hydrogen carbonate,azodicarboxylic acid diamide, dicyandiamidine nitrate, dicyandiamidinesulfate, tetrazene, and semicarbizide nitrate; an oxidizing agentcomprising a peroxide or comprising a mixture of a peroxide and anitrate; and coolants, reducing agents and catalysts; wherein thereaction products of the propellant composition do not contain toxicgases in health-endangering concentrations.
 6. A propellant compositionaccording to claim 5, wherein the reaction products of the propellantcomposition do not contain toxic gases in excess of at least one of MAKand TLV values.
 7. A propellant composition for producing reactionproducts not having toxic gases in health-endangering concentrations ingas generators, the components of the composition consisting essentiallyof: at least one nitrogen-containing compound selected from the groupconsisting of (a) tetrazole or a tetrazole derivative of the formulae IAor IB:

 wherein R₁ and R₂ or R₃ are identical or different and are hydrogen,hydroxy, amino, carboxy, an alkyl residue of 1-7 carbon atoms, analkenyl residue of 2-7 carbon atoms, an alkylamino residue of 1-10carbon atoms, an aryl residue, an arylamino residue, a substituted arylresidue or a substituted arylamino residue, the substituted aryl residueor substituted arylamino residue being substituted by one or severalsubstituents which are identical or different, and which are selectedfrom the group consisting of an amino group, a nitro group and an alkylgroup of 1-4 carbon atoms or a sodium, a potassium or a guanidinium saltof said tetrazole or tetrazole derivative, and (b) at least one compoundselected from the group consisting of (A) a cyanic acid derivativeselected from the group consisting of sodium cyanate, cyanuric acid,1-cyanoguanidine, disodium cyanamide and a salt of sodium cyanamide, (B)triazine or triazine derivative selected from the group consisting ofcyanuric acid ester, cyanuric acid amide and their salts, and (C) urea,its salts and a urea derivative selected from the group consisting ofbiuret, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine,aminoguanidine nitrate, aminoguanidine hydrogen carbonate,azodicarboxylic acid diamide, dicyandiamidine nitrate, dicyan-diamidinesulfate, tetrazene, and semicarbizide nitrate; an oxidizing agentcomprising a peroxide or comprising a mixture of a peroxide and anitrate; and ferrocene as a catalyst; wherein the reaction products ofthe propellant composition do not contain toxic gases inhealth-endangering concentrations.
 8. A propellant composition accordingto claim 7, wherein the reaction products of the propellant compositiondo not contain toxic gases in excess of at least one of MAK and TLVvalues.
 9. A propellant composition for producing reaction products nothaving toxic gases in health-endangering concentrations in gasgenerators, the components of the composition consisting essentially of:(1) at least one nitrogen-containing compound selected from the groupconsisting of tetrazole or a tetrazole derivative of the formulae IA orIB:

 wherein R₁ and R₂ or R₃ are identical or different and are hydrogen,hydroxy, amino, carboxy, an alkyl residue of 1-7 carbon atoms, analkenyl residue of 2-7 carbon atoms, an alkylamino residue of 1-10carbon atoms, an aryl residue, an arylamino residue, a substituted arylresidue or a substituted arylamino residue, the substituted aryl residueor substituted arylamino residue being substituted by one or severalsubstituents which are identical or different, and which are selectedfrom the group consisting of an amino group, a nitro group and an alkylgroup of 1-4 carbon atoms or a sodium, a potassium or a guanidinium saltof said tetrazole or tetrazole derivative, and (2) an oxidizing agent,wherein the oxidizing agent is an inorganic peroxide or comprising amixture of an inorganic peroxide and a nitrate; wherein the reactionproducts of the propellant composition do not contain toxic gases inhealth-endangering concentrations.
 10. A propellant compositionaccording to claim 9, wherein the reaction products of the propellantcomposition do not contain toxic gases in excess of at least one of MAKand TLV values.